Metallic sintering compositions including boron additives and related methods

ABSTRACT

The disclosure relates to sintering compositions that can be used in three-dimensional printing or additive manufacturing processes. The sintering compositions generally include one or more metallic iron-containing powders and a minor amount of a boron-containing powder as a sintering aid. Sintered models or products formed from the sintering compositions have substantially improved density and surface roughness values relative to models formed without the boron-containing powder.

CROSS REFERENCE TO RELATED APPLICATION

Priority is claimed to U.S. Provisional Application No. 62/346,695 filedJun. 7, 2016, which is incorporated herein by reference in its entirety.

STATEMENT OF GOVERNMENT INTEREST

None.

BACKGROUND OF THE DISCLOSURE Field of the Disclosure Background

Current three-dimensional printing techniques utilizing sintering of abinder-fixed sintering model typically achieve a final density of about50%-60% of the theoretical density of an iron-based sintered powder. Theresulting sintered product is then infiltrated with a bronze alloythrough capillary action to increase the product density. Theinfiltrated and sintered product, however, does not have uniformcomposition and can be unsatisfactory in terms of material propertiesfor much application (e.g., mechanical or tensile properties, electricalproperties, thermal properties, etc.).

SUMMARY

In an aspect, the disclosure relates to a sintering compositioncomprising (e.g., consisting essentially of or consisting of) inadmixture: (a) a first metallic iron-containing powder; (b) aboron-containing powder; and (c) (optionally) a second metalliciron-containing powder having at least one of a different compositionrelative to the first metallic iron-containing powder and a differentsize distribution relative to the first metallic iron-containing powder(e.g., a number-, mass-, or volume-average size or diameter that isdifferent between the first and second powders). In a refinement, thesecond metallic iron-containing powder is present; and the firstmetallic iron-containing powder and the second metallic iron-containingpowder are present in a weight ratio in a range from 1:10 to 10:1 (e.g.,1:9 to 9:1, 1:8 to 8:1, 1:6 to 6:1, 1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1,or 1:1.5 to 1.5:1). In another refinement, the second metalliciron-containing powder is present; and the first metalliciron-containing powder and the second metallic iron-containing powderhave a different size distribution from each other. For example, thefirst metallic iron-containing powder and the second metalliciron-containing powder can have the same composition and together form abimodal size distribution of the same composition.

Various refinements of the sintering composition are possible.

In a refinement, the first metallic iron-containing powder and thesecond metallic iron-containing powder (when present) independentlycomprise iron-containing metallic alloy particles (e.g., same ordifferent kind of alloy particles for the first and second powders; suchas containing at least 50, 60, 70, 80, 90, or 95 wt. % iron andoptionally one or more of carbon, manganese, aluminum, chromium, copper,nickel, molybdenum, silicon, vanadium). For example, the first metalliciron-containing powder and the second metallic iron-containing powder(when present) can independently comprise stainless steel particles(e.g., same or different kind of stainless steel particles for the firstand second powders). Similarly, the first metallic iron-containingpowder and the second metallic iron-containing powder (when present) canindependently comprise steel particles (e.g., same or different kind ofsteel particles for the first and second powders). In anotherrefinement, the boron-containing powder comprises one or more ofelemental boron particles, boron carbide (BC) particles, and boronnitride (BN) particles.

In a refinement, the first metallic iron-containing powder and thesecond metallic iron-containing powder (when present) are togetherpresent in an amount from 90 wt. % to 99.99 wt. % relative to thesintering composition (e.g., at least 90, 95, 98, 99, 99.9 wt. % and/orup to 95, 98, 99, 99.9 or 100 wt. % concentration in the sinteringcomposition). In another refinement, the boron-containing powder ispresent in an amount from 0.01 wt. % to 10 wt. % relative to thesintering composition (e.g., at least 0.01, 0.1, 0.2, 0.5, or 0.8 wt. %and/or up to 1, 1.2, 1.5, 2, 5, 8, or 10 wt. % concentration in thesintering composition, such as 0.2 wt. % to 2 wt. %). In anotherrefinement, the first metallic iron-containing powder, theboron-containing powder, and the second metallic iron-containing powder(when present) are together present in an amount from 90 wt. % to 100wt. % relative to the sintering composition (e.g., at least 90, 95, 98,99, 99.9, 100 wt. % and/or up to 95, 98, 99, 99.9 or 100 wt. %concentration in the sintering composition).

In a refinement, the first metallic iron-containing powder and thesecond metallic iron-containing powder (when present) independently havea particle size in a range from 1 μm to 100 μm (e.g., a number-, mass-,or volume-average size or diameter, such as at least 1, 2, 5, 10, or 20μm and/or up to 10, 20, 40, 50, 80, or 100 μm; same or different sizeparameter for the first and second powders). For example, the firstmetallic iron-containing powder can have a particle size in a range from10 μm to 50 μm (e.g., 20 μm to 40 μm); and the second metalliciron-containing powder can be present and have a particle size in arange from 1 μm to 20 μm (e.g., 2 μm to 10 μm). Alternatively oradditionally, the second metallic iron-containing powder can be present;and the first metallic iron-containing powder and the second metalliciron-containing powder can have average sizes (number-, mass-, orvolume-average sizes) in a ratio in a range from 1.5:1 to 10:1 (e.g., atleast 1.5:1, 2:1, or 3:1 and/or up to 3:1, 5:1, 8:1, or 10:1 with thefirst powder having the larger average size). In another refinement, theboron-containing powder has a particle size in a range from 0.01 μm to20 μm (e.g., a number-, mass-, or volume-average size or diameter, suchas at least 0.01, 0.1, 0.2, 0.5, or 1 μm and/or up to 1, 2, 3, 5, 10, or20 μm, for example 0.1 μm to 3 μm or 0.2 μm to 2 μm). In anotherrefinement, the first metallic iron-containing powder and theboron-containing powder have average sizes (number-, mass-, orvolume-average sizes) in a ratio in a range from 5:1 to 100:1 (e.g., atleast 5:1, 10:1, 15:1, or 20:1, or 30:1 and/or up to 30:1, 50:1, 80:1,or 100:1 with the first powder having the larger average size).

In another aspect, the disclosure relates to a sintering modelcomprising: the sintering composition according to any of the variouslydisclosed embodiments; and a (cured) binder phase distributed throughoutthe sintering composition (e.g., a composite structure with the binderphase being distributed between adjacent powder particles in thesintering composition). In a refinement, the binder phase comprises apolymeric binder (e.g., a cureable or cured polymeric binder or resin,for example a crosslinkable or crosslinked binder or resin; cured binderor resin is degradable at an intermediate temperature between its curingtemperature and the sintering temperature; an example binder systemincludes ethylene glycol monobutyl ether, ethylene glycol, andisopropanol).

In another aspect, the disclosure relates to a method for forming afused or sintered model, the method comprising: sintering the sinteringmodel according to any of the variously disclosed embodiments to form aunitary fused model from the sintering composition. Sintering generallyincludes applying heat and/or pressure a level and time sufficient tofuse the powder components of the sintering composition withoutsubstantial melting such as to liquefaction. Sintering can be performedunder a vacuum or under an inert gas atmosphere (e.g., argon atmosphere)in order to avoid oxidation of the composition components duringsintering. Sintering is suitably performed at a temperature sufficientto decompose/eliminate the binder from the model. In some embodiments, apre-sintering step is performed after the binder is cured. Thepre-sintering is performed at a temperature sufficient todecompose/eliminate the cured binder from the model, but less than atemperature sufficient to fully sinter the model (e.g., at least 200°C., 300° C., or 400° C. and/or less than 600° C., 800° C., or 1000° C.).At such decomposition temperatures, partial sintering of some powerparticles occurs to a degree sufficient to maintain the shape of thesintering model even in the absence the cured binder (albeit at a lowdensity and with low tensile strength properties), which partiallysintered model can be fully sintered at higher temperatures.

In another aspect, the disclosure relates to a method for forming afused or sintered model, the method comprising: (a) providing a sampleof the sintering composition according to any of the variously disclosedembodiments (e.g., sample can be any shape or size, such as a thin layerof sintering composition powder); (b) applying a binder to at least aportion of the sintering composition sample; (c) optionally repeating(a) and (b) a plurality of times, wherein (i) successive sinteringcomposition samples are provided and applied to the previous sinteringcomposition sample, (ii) successive sintering composition samples can bethe same or different size and/or shape, and (iii) successive portionsof applied binder can be the same or different size and/or shape; (d)curing the binder and then removing free sintering composition frombound sintering composition to form a sintering model (e.g., removal offree, flowable sintering composition powder not fixed by the curedbinder in the bound sintering composition); and (e) sintering thesintering model to form a unitary fused model from the sinteringcomposition. In a refinement, the sintering composition sample is in theform of a thin layer (e.g., at least 0.01, 0.02, 0.05, or 0.1 mm and/orup to 0.1, 0.2, 0.5, 1, 2, or 5 mm, such as 0.02 mm to 1 mm; successivesamples in a multi-sample process can have same or different layerthicknesses). In another refinement, curing the binder comprisesperforming one or more of applying heat to the binder, exposing thebinder to light (e.g., ultraviolet light of a UV-cureable binder resin),exposing the binder to oxygen and/or water (e.g., expose to air, such asfor moisture- or oxidation-cureable resins). In another refinement, themethod comprises performing (c) as part of a three-dimensional printingprocess (e.g., applying successive sintering composition samples assuccess layers in an adjustable print bed and applying successiveportions of binder with a moveable print head).

In another aspect, the disclosure relates to a method for forming afused or sintered model, the method comprising: (a) providing a sampleof the sintering composition according to any of the variously disclosedembodiments (e.g., sample can be any shape or size, such as a thin layerof sintering composition powder); (b) locally sintering at least aportion of the sintering composition sample (e.g., using a localized orpoint-wise source of heat or energy, such as a laser, electron beam,etc.); (c) optionally repeating (a) and (b) a plurality of times,wherein (i) successive sintering composition samples are provided andapplied to the previous sintering composition sample, (ii) successivesintering composition samples can be the same or different size and/orshape, and (iii) successive portions of locally sintered composition canbe the same or different size and/or shape; and (d) removing freesintering composition from locally sintered composition to form a fusedmodel. In a refinement, the sintering composition sample is in the formof a thin layer (e.g., at least 0.01, 0.02, 0.05, or 0.1 mm and/or up to0.1, 0.2, 0.5, 1, 2, or 5 mm, such as 0.02 mm to 1 mm; successivesamples in a multi-sample process can have same or different layerthicknesses). In another refinement, the method comprises performing (c)as part of a three-dimensional printing process (e.g., applyingsuccessive sintering composition samples as success layers in anadjustable print bed and locally sintering successive portions ofcomposition with an adjustable localized or point-wise source of heat orenergy head).

Various refinements of the sintering and fusing methods as well as theresulting fused model are possible.

In a refinement, sintering comprises heating to a temperature in a rangefrom 1100° C. to 1300° C. (e.g., 1150° C. to 1250° C.). In anotherrefinement, the fused model has a surface roughness less than that of acorresponding fused model formed without the boron-containing powder(e.g., at least a 10, 20, or 30% reduction and/or up to a 20, 40, 60, or80% reduction in surface roughness). In another refinement, the fusedmodel has a surface roughness in a range from 1 μm to 9 μm (e.g., atleast 1, 2, 3, or 5 μm and/or up to 6, 7, 8, or 9 μm). In anotherrefinement, the fused model has a density that is greater than that of acorresponding fused model formed without the boron-containing powder(e.g., at least a 10, 20, or 30% increase and/or up to a 20, 30, or 40%increase in density). In another refinement, the fused model has adensity of at least 80% relative to the theoretical density of thesintering composition (e.g., at least 80, 85, 90, 95, or 98% and/or upto 90, 95, 98, 99, or 100% of the theoretical density of the sinteringcomposition/metallic powder components thereof, where theoreticaldensity is the density of a continuous, non-porous sample of thesintering composition/metallic powder components).

In another aspect, the disclosure relates to a unitary fused modelhaving any of the foregoing characteristics, for example formedaccording to any of the variously disclosed methods and using any of thevariously disclosed sintering compositions and/or models.

While the disclosed compounds, methods and compositions are susceptibleof embodiments in various forms, specific embodiments of the disclosureare illustrated (and will hereafter be described) with the understandingthat the disclosure is intended to be illustrative, and is not intendedto limit the claims to the specific embodiments described andillustrated herein.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the disclosure, reference should bemade to the following detailed description and accompanying drawingswherein:

FIG. 1 is a schematic illustrating a three-dimensional printing oradditive manufacturing process according to the disclosure.

FIG. 2 includes graphs illustrating (1) densification/displacement (μm)and (2) furnace temperature profile (° C.) for a sintered cube formedaccording to the disclosure during (A) heating and holding in zone 1 and(B) cooling in zone 2.

FIG. 3 includes optical microscope images illustrating themicrostructure of sintered product samples formed according to thedisclosure for samples including (A) 0.5% boron sintered at 1150° C.(scale bar: 50 μm), (B) 0.5% boron sintered at 1200° C. (scale bar: 50μm), and (C) 0.5% boron sintered at 1250° C. (scale bar: 100 μm).

FIG. 4 includes confocal laser scanning microscope images illustratingthe topography of sintered product samples formed according to thedisclosure for samples sintered at 1250° C. and including (A) 0.5% boroncarbide, (B) 0.5% boron nitride, and (C) no boron additive (i.e., purestainless steel).

FIG. 5 includes images illustrating undistorted of sintered cubes formedaccording to the disclosure for samples sintered at 1250° C. andincluding (A) 0.5% boron carbide, (B) 0.5% boron nitride, and (C) noboron additive (i.e., pure stainless steel).

FIG. 6 includes images illustrating distorted of sintered cubes formedaccording to the disclosure for samples sintered at 1250° C. andincluding (A) 1.5% boron, (B) 1.5% boron nitride, and (C) 1.5% boroncarbide.

DETAILED DESCRIPTION

The disclosure relates to sintering compositions that can be used inthree-dimensional printing or additive manufacturing processes. Thesintering compositions generally include one or more metalliciron-containing powders and a minor amount of a boron-containing powderas a sintering aid. Sintered models or products formed from thesintering compositions have substantially improved density and surfaceroughness values relative to models formed without the boron-containingpowder.

In current additive manufacturing (AM) processes, it is difficult toobtain a combination of high structural integrity, complexity, anddesirable scales in the formed part/product from the AM process. Scalemeans both volume (size) and quantity of the formed part, while thecomplexity relates to both the geometric complexity as well as thecustomization of the formed part. A part requiring high structuralintegrity is not easy to produce using AM at the present time. A simplesolution to increase in the scale is to increase the working environmentor to operate many machines in parallel. However, the integrity requiresthe AM fabrication to make a product with the material whose strength iscomparable to the material produced in traditional manufacturingprocesses. This is the major challenge within the AM community.

Many types of powder-based AM systems are currently available. Suchsystems include three-dimensional (3D) printing (3DP), selective lasersintering (SLS), selective laser melting (SLM) and electron beam melting(EBM). These powder-based systems can be distinguished based on twoconsolidation methods: local and uniform heating. Immediately, the localheating methods such as SLS, SLM and EBM are the main source ofinhomogeneity in AM parts. These methods may typically achieve a muchhigher final density (although not reaching a theoretical densitycompletely) because the material is melted and consolidated with aheating source such as laser or electron beam. Then, during the printingprocess, the consolidated material below is altered while the materialabove is consolidating. Therefore, the microstructure is extremelynon-uniform and sometimes the residual stresses can be too intense toform cracks in the processed material. This problem can be mitigated byraising the temperature during printing or heat-treating and/orhot-isostatic pressing (HIP-ing) afterwards to minimize thesedetrimental defects as well as voids. 3DP is one of the few methodswhere a part can undergo uniform heating, resulting in a more uniformfinal microstructure. However, the primary drawback of 3DP is itstypical inability to achieve a high relative density, which in turn canadversely affect the final material properties of the formed part.

In most processes, the relative density of metallic green parts obtainedby 3DP can reach about the 50-60% of a theoretical density. This resultis much lower than the green compacts made via powder metallurgy (P/M),which enables up to the 85% of a theoretical density. In general, thedensity of a part made from 3DP is much lower than that made form P/Mtechnique. Thus, a post-processing step is necessary to improve thefinal density of a 3D printed part using current methods. After 3Dprinting, a part is typically infiltrated with a low melting metallicmaterial such as bronze, which changes the nature of the material whileslightly improving the mechanical properties such as elastic modulus,yield strength, hardness etc. by filling in the pores of the printedmaterial. A few other techniques for making high-dense homogeneous 3DPparts have been published. One of them was the method of infiltratingtransient liquid phase that combines through diffusion with the skeletalmaterial to form a desirable final composition. The disadvantage of thisinfiltration method is that in increases the cost of the entire process.A fine carbonyl nickel powder (size 5 μm) has been used to print parts,and then sinter the parts in order to reach 92% relative density.

The static properties such as hardness, yield strength and elasticmodulus of an AM part must reach those of a traditionally processed partif they are expected to use in real applications. Moreover, an AM partis noticeably lacking in its fatigue properties. Instead of the costlymeasurement of the physical properties of the materials after AM, thedensity of the sintered product samples can be evaluated to representoverall physical properties of the final product. As illustrated in theexamples below, stainless steel 420 (SS420) powder was mixed withvarious compounds as possible sintering aids to improving the finaldensity, which is the first step toward improving the integrity of 3DPparts. This approach can allow fabrication of functional parts, alsoknown as direct digital manufacturing using the powder-based system. Oneof few machines available in the current market that provide a uniformconsolidation condition is 3DP units manufactured by EXONE (N.Huntingdon, Pa.). This system contains two powder beds: supply andprint. The part building process for this device is based on depositinglayer by layer of powder while injecting a binder phase at the datapoints from the given STL file. The required STL file can be createdfrom the simple conversion of a CAD part file.

Previous work demonstrated the effectiveness of ceramic sintering aidsfor enhancing sintered samples printed from 420 stainless steel. Siliconnitride powder was mixed with stainless steel powder, which resulted ina high relative density (˜98%) and excellent mechanical properties (near200 GPa) sintering at 1300° C. with slight distortion on the 3D printedpart. However, because of the large amount of silicon nitride (12.5 wt %equivalent to 28% volume), the part may not have been considered to be astainless steel.

In order to reduce the amount of additive utilized, boron-based powdersincluding boron (B), boron nitride (BN) and boron carbide (BC) wereevaluated and compared. According to the phase diagram of iron-boron,1174° C. is the liquid-phase formation at eutectic temperature. Its lowmelting temperature is advantageous because sintering could be performedat a relatively low temperature. In P/M experiments, only 0.4 wt % ofboron was added to 316 stainless steel and sintered at 1240° C., whichresulted in 99% density. As illustrated in the examples below, thedensification test for many samples at different locations in the powderbed was conducted to test the homogeneity of printed parts. To improvethe surface finish, small particle sizes for the additives were selectedto fill in the gaps of the larger particles (e.g., stainless steel basepowder particles) in order to increase surface quality and smoothness ofthe final part.

FIG. 1 illustrates the formation and use of a sintering composition 100according to the disclosure to form a corresponding sintering modeland/or sintered or fused model (e.g., a unitary fused model). Thesintering composition 100 includes a first metallic iron-containingpowder 110 and a boron-containing powder 120 in admixture, which powderscan be suitably blended in a (dry) mixer. Other desired components ofthe sintering composition 100, such as a second metallic iron-containingpowder (not shown) or otherwise, can be mixed with the metalliciron-containing powder 110 and the boron-containing powder 120. Asuitable apparatus for forming a sintering model is illustrated in FIG.1 as a three-dimensional printing apparatus 200 including a supply bed210, a print bed 220, a print head 230 adapted to deliver a binder 240(e.g., with the print head 230 containing the binder 240 or being influid connection with a binder 240 reservoir (not shown)), and a roller250. A supply of the sintering composition 100 is placed in the supplybed 210, and a first sample 102 a of the sintering composition 100 isdelivered via the roller 250 to the print bed 220 as a thin layer of thesintering composition 100. Binder 240 is then selectively applied viathe print head 230 to a portion 102 b of the sintering composition 100first sample 102 a. The print bed 220 is then lowered (e.g., via amoveable lower supporting surface therein), and a second sample 104 a ofthe sintering composition 100 is delivered via the roller 250 to theprint bed 220 as a thin layer of the sintering composition 100 sittingon top of the previous first sample 102 a and binder-containing portion102 b thereof. Similarly, further binder 240 is then selectively appliedvia the print head 230 to a portion 104 b of the sintering composition100 second sample 104 a. The process of adding additional layers/samplesof the sintering composition 100 with corresponding binder-containingportions can be repeated as desired to build a corresponding sinteringmodel 300 in which the collective binder-containing portions of thesintering composition 100 generally define the geometry of the sinteringmodel 300 and eventual sintered or fused model. Preferably, the binder240 in the sintering model 300 is cured (e.g., via exposure to heat,light, oxygen, water, etc.) and excess free sintering composition 100 isthen removed (e.g., as a free-flowing powder). The sintering model 300(e.g., with a cured binder 240 and without excess sintering composition100 powder) can then be placed in a suitable furnace (not shown), wherethe sintering model 300 can be sintered as a whole at a selectedtemperature. In other embodiments (not illustrated in FIG. 1), abinder-less method of sintering can be used in which a sample of thesintering composition 100 is locally sintered at selected portions(e.g., using a localized or point-wise source of heat or energy, such asa laser, electron beam, etc.), which portions are selected to correspondto the desired geometry of the final fused or sintered model.

EXAMPLES

The following examples illustrate the disclosed sintering compositions,sintering models, and related three-dimensional printing or additivemanufacturing methods, but are not intended to limit the scope of anyclaims thereto.

The examples illustrate the ability of the disclosed compositions andmethods to attain fully dense parts with a powder-based 3D printingmethod by sintering, instead of following the standard protocol ofinfiltrating bronze. Example ingredients that can be added to improvethe densification were tested, which will also enhance the structuralintegrity of 3D printed 420 stainless steels (SS). As already applied inthe field of powder metallurgy (P/M), a small addition of ingredients(sintering aid) into a base metal powder enhances densification andimproves the final structural integrity. Numerous P/M works havesuggested possible ingredients as sintering aids, but did not performtests with a consistent set of experimental conditions. These examplesuse a consistent set of experimental conditions, including the use of420 stainless steel (SS) as a base powder, which is common for 3Dprinting, with an average size of 30 micron. The base powder wassintered between 1150 and 1250° C. after the powder was mixed withvarious sintering ingredients, including various boron-containingpowders. Each sintered sample was analyzed in terms of the final densityattained, the amount of ingredient mixed, and the sintering temperature.

Materials: Spherical stainless steel 420 SS powder (available fromEXONE, N. Huntingdon, Pa.) was used in all experiments as the basepowder. 420 SS has a particle size distribution range between 22 μm and53 μm and with a mean size of 30 μm. Three additives, boron (B), boroncarbide (BC) and boron nitride (BN), were used as sintering aids, andtheir material specifications were provided in Table 1.

TABLE 1 Additives Material Specification Average Particle DensityMaterial Provider Size (μm) (g/cm³) B Sigma Aldrich 1 2.34 BC Panadyne0.6 2.51 BN Sigma Aldrich 1 2.29

For each sintering aid, three experiments were conducted with 0.5 wt %,1.0 wt % and 1.5 wt % of additive with the balance being 420 SS as thebase powder, with one additional comparison sample batch that containedno additives (i.e., 100 wt. % 420 SS). During each experiment (printingbatch), 400 grams of powder mixture was measured and mixed. All powderswere measured using ADVENTURER AR 2140 (Ohaus Corp., Parsippany, N.J.,USA) which has a resolution of 0.0001 g. A speed mixer DAC 150(FlackTek, Inc., Landrum, S.C., USA) was then used to mix the powdermixture with angular velocity of 2000 rpm and 90 seconds per cycle forthree cycles. For the density and densification rate experiments, 9cubic samples were printed, each with dimensions of 8 mm by 8 mm by 8mm.

Sample Preparation: The printing process for the tested samples used anX1-LAB 3D printer (available from EXONE, N. Huntingdon, Pa.). Asgenerally shown in FIG. 1, this machine operates through the use of twobeds: a supply bed and a print bed. Prior to the printing process, thesupply bed is lowered as far as it can and filled with the prescribedpower mixture. This ensures that the machine can print as many layers asa design requires. The print bed, however, is raised to the top, so thelayers of powder can easily be moved onto it. Once the printing processhas begun, a roller moves a layer of power (0.1 mm) from the supply bedand layers a layer to the print bed. The machine then lays down a binderphase on top of the layer. Once the next layer is ready to be laid down,the supply bed is raised, so the appropriate amount of powder isexposed, and the print bed is lowered, so the new layer can easily bemoved on to it. This process is repeated until the part is completed. Inthe printing process, the amount of binder phase on each layer has to becontrolled such that the layer can bind to the previous layer to form afinal shape of a part.

Density Variation: The deposition variation within the print bed was thefirst concern. This could result in size variation depending on thelocation of a part printed in the powder bed. To investigate thispossibility, nine small cubes were printed and the shrinkage on eachcube was measured in a real time while sintering using athermomechanical analyzer (TMA) (EVOLUTION 18, available from Setsys,France) under the protective environment of argon gas. The finalsintering temperature was set at 1400° C. for 6 hours with a temperaturerate of 10° C./min for both heating and cooling cycles, and the finalcooling temperature was set at a room temperature.

Sintering: A Materials Research Furnaces (MRF; Allenstown, N.H.)environment-controlled furnace was used to sinter the 3D printedsamples. The furnace utilized argon gas to avoid oxidation. Byextracting the gas in the furnace before the sintering begins, theoxidation of the samples was prevented. For the experimental process,the 3D printed samples were separated depending on the sinteringtemperature. The three sintering temperatures were 1150° C., 1200° C.,and 1250° C. In order to reach the sintering temperatures, the sampleswere placed in the furnace, and the heating process was started at roomtemperature. The furnace then began to heat samples to 240° C. at a rateof 10° C./min. Once the furnace reached 240° C., it was kept at thistemperature for 2 hour to burn out the binder phase. The binder phaseconsists of ethylene glycol monobutyl ether, ethylene glycol andisopropanol which are expected to burn out at the temperatures of 170°C., 197.3° C. and 82.6° C., respectively. Thus, at 240° C., these binderphase is completely eliminated. Then, the furnace was heated to eachprescribed sintering temperature from 240° C. at a rate of 5° C./min.Once the samples reached their prescribed sintering temperature, theywere kept at this temperature for 6 hours to complete the sinteringprocess of the samples. The samples were then cooled back down to roomtemperature at a rate of 10° C./min. In order to calculate the relativedensity, the volume of each fully sintered piece was measured byArchimedes' principle using an ADVENTURER AR 2140 scale (Ohaus Corp.,USA), which has a resolution of 0.0001 g.

Results—Density Variation: Each 3D-printed cube was labeled #1 to #9,based on its location in a 3×3 matrix to test spatial density within agenerally horizontal plane. During printing, the overall layout wascentered to the print bed and each part was spaced evenly; thus cube #5was the origin, (0,0). All other cubes were either 1 unit away inhorizontal direction or vertical direction or both (i.e., transverse andlateral directions in a plane perpendicular to the axial printingdirection), and their coordinates were assigned accordingly (e.g., cube#1 was at position (−1,1)). After the printing process, the printedsamples are very close in the printed dimensions. In order to see thedensity variation among these samples, the samples were sintered at1400° C. in the TMA.

All samples had similar densification profiles as shown in FIG. 2. Thisis the densification of the cube 1. Each profile was separated into twozones: zone 1 (heating and holding) and zone 2 (cooling). FIG. 2includes both temperature and densification profiles during the timespan. The shrinkage starts at 1200° C. and the shrinkage rate increasesmuch faster when the temperature reaches 1400° C. The samples continueto shrink in cooling process, so the density of the final sample may beincreased by increasing the soaking time (6 hours).

A correlation matrix (ranging from −1 to 1) was computed and shown inTable 2 to analyze the relationship between the printed location of eachcube and the correlation in shrinkage, both maximum shrinkage andshrinkage at 1400° C. Shrinkage was converted to positive value prior tothe analysis. A significant negative correlation between the shrinkageand horizontal direction indicated that shrinkage increases as thelocation of cube moves to the left (negative direction); and near tozero correlation between the shrinkage and vertical direction impliedthat vertical location was not a significant factor for shrinkage. Asthe roller spread the power from the right side of power bed to the leftside, the right side of the powder bed had a higher compact factor sincemore powder exists at the beginning (the right side) on each layer thanat the end (the left side). Therefore, the parts printed on the leftside of the powder bed would experience more shrinkage as observedduring TMA experiment.

TABLE 2 Correlation Matrix of Shrinkage in Horizontal & VerticalDirections Correlation in Correlation in Maximum Shrinkage Shrinkage at1400° C. Horizontal Direction −0.8205 −0.71688 Vertical Direction0.052274 0.133584

Results—Liquid Phase Sintering: Each sample was polished using a diamondpolishing solution with a grit size of 1 μm for 30 minutes and etchedwith the solution made of 10 mL HNO₃, 20 mL HCl and 30 mL water for afew seconds. Then it was examined under optical microscope to visualizethe microstructure. FIG. 3 (panels A, B, C) shows the microstructures ofthe samples with 0.5% of B additives sintered at (A) 1150° C., (B) 1200°C. and (C) 1250° C., respectively. FIG. 3(B) shows that the samplessintered at 1200° C. had liquid phase present as powders started togroup themselves, as compared to FIG. 3(A) where the powders in theiroriginal spherical shapes remained the same. FIG. 3(C) shows theformation of much larger grains and grain boundaries. It indicates thatthe grains have coalesced into larger grains. FIG. 3(C) also showsnecklace microstructure between grains, an indication of liquid phasesintering. Similar microstructure behavior can be observed in thesamples with the other two additives sintered at higher temperature,where liquid phase sintering started to occur based on the presence ofthe necklace microstructure.

Results—Surface Quality: One of the important issues with 3D printing isthe surface quality. Because of its characteristic building process, thelayering is evident on the side surfaces of the printed part. Itimproves little after sintering. Using a powder with a bimodal sizedistribution, it is possible increase not only the density of the sample(because the multiple powder sizes can increase the packing density) butalso the surface quality of the samples. However, sometimes the mixingtwo distinct powders is difficult. The slurry method is used with abimodal powder because small particles are difficult to be spread whenthey are dry and the amount of fine powder is generally more than 25 wt.% (i.e., with 75 wt. % or less coarse powder relative to total powder)with previous approaches to using bimodal powders. However, theseexamples used only small amounts of fine additive powder (i.e., 0.5-1.5wt. % boron-based additive with average sizes between 0.6-1 μm), and thehigh speed mixing process described above was very effective.

The surface roughness of each sample after sintering was measured by aZeiss LSM 210 Confocal Laser Scanning Microscope. FIG. 4 shows thetopography of three sintered samples at 1250° C. with (A) 0.5% boroncarbide, (B) 0.5% boron nitride, and (C) pure stainless steel. Thesurface roughness decreases significantly in the samples with theadditives. Especially, the sample with 0.5% boron carbide sintered at1250° C. formed a liquid phase and provided a smooth surface. Theaverage roughness value, Ra, improved from 9.01 μm with pure stainlesssteel to 8.2 μm with 0.5% boron nitride and 6.22 μm with 0.5% boroncarbide.

Results—Densification: The SS420 powder samples were mixed with the0.5%, 1% and 1.5% by weight of the three additives: boron (B), boronnitride (BN), and boron carbide (BC). Each of these samples was sinteredat the temperatures of 1150° C., 1200° C. and 1250° C. The density ofeach sample after sintering was measured using the Archimedes principle.As shown in Table 3, the additives did not necessary increase thedensity of the samples after sintering at 1150° C. Raising the sinteringtemperature from 1150° C. to 1200° C. and 1250° C. increased thedensities in each case. For each sintering temperature, it was foundthat the samples with 1% wt B additives had the highest densities. Amongthe samples with BN additives, the samples with 1% wt BN additive hadthe highest densities. The highest relative density was attained withthe sample with 1% wt B additive at approximately 97%. There was adramatic drop in the relative density from the 1% wt of B to the 1.5% wtof B at 1250° C. because the latter sample formed extensive liquid phaseduring sintering. With the presence of the extensive liquid phase, poreswere generated. The liquid phase caused the distortion in the sampleswith 1.0% wt B and BC additives at both 1200° C. and 1250° C., and thesample with 1.0% wt BN additives at 1250° C. The samples with 1.5% wt ofall additives sintered at 1250° C. exhibited shape distortion. Thedistortion was based on the observation of the shape of the cubicsamples as illustrated in FIGS. 5 (no shape distortion) and 6 (moderateto extensive shape distortion). The sample with 0.5% wt of B additivesintered at 1250° was also distorted (not shown in figures). The samplewith 0.5% wt of BN and BC sintered at 1250° C. remained the same shapeas shown in FIG. 5 (panels A and B). The sample with the highest densitythat maintainedits shape was the 0.5% BC sample sintered at 1250° C.with a relative density of 90.22%.

TABLE 3 Final Relative Densities After Sintering with and withoutAdditives Relative Density Boron Boron Nitride Boron Carbide Sintered at0.5% 1.0% 1.5% 0.5% 1.0% 1.5% 0.5% 1.0% 1.5% No additive 1150° C. 52.95%55.33% 54.56% 51.80% 53.58% 49.74% 53.35% 53.33% 50.24% 55.32% 1200° C.77.82% 83.02% 68.34% 59.31% 77.72% 56.10% 75.80% 74.83% 65.79% 63.16%1250° C. 90.70% 96.98% 80.57% 87.62% 91.41% 90.18% 90.22% 93.97% 83.46%64.58%

Summary: The 3D printing and sintering process were used to make partsfrom SS420 stainless steel powder with boron-based additives. The effectof additive contents and sintering temperature were evaluated based onthe relative densities of the final parts. (1) A slight variation in thedensification rate of samples depended on the locations in the printbed. It can be explained by the variation in the powder packing as theroller moves from the right to the left. More powder is present at theright side of the print bed during the powder spreading. (2) The powdersamples mixed with the smaller additives helped to improve the finalsurface finish substantially. Not only did the smaller additives fillinto the interstitial spaces among large based powder particles, butalso the additives enhanced diffusion among the stainless steels powder.(3) The highest density obtained was 97% with the sample containing 1%boron and sintered at 1250° C. However, the sample was extensivelydistorted because of the extensive formation of liquid phase. (4) Thedensest sample that maintained the original shape without distortion wasthe 0.5 wt. % boron carbide sintered at 1250° C. with the relativedensity of 90.22%. (5) The extensive distortion is evident with theboron (B only) additive. By reducing the sintering temperature, the useof the boron additive may improve the final shape.

Because other modifications and changes varied to fit particularoperating requirements and environments will be apparent to thoseskilled in the art, the disclosure is not considered limited to theexample chosen for purposes of illustration, and covers all changes andmodifications which do not constitute departures from the true spiritand scope of this disclosure.

Accordingly, the foregoing description is given for clearness ofunderstanding only, and no unnecessary limitations should be understoodtherefrom, as modifications within the scope of the disclosure may beapparent to those having ordinary skill in the art.

All patents, patent applications, government publications, governmentregulations, and literature references cited in this specification arehereby incorporated herein by reference in their entirety. In case ofconflict, the present description, including definitions, will control.

Throughout the specification, where the compounds, compositions,methods, and processes are described as including components, steps, ormaterials, it is contemplated that the compositions, processes, orapparatus can also comprise, consist essentially of, or consist of, anycombination of the recited components or materials, unless describedotherwise. Component concentrations can be expressed in terms of weightconcentrations, unless specifically indicated otherwise. Combinations ofcomponents are contemplated to include homogeneous and/or heterogeneousmixtures, as would be understood by a person of ordinary skill in theart in view of the foregoing disclosure.

REFERENCES

1. Allen, S M & Sachs, EM 2000, ‘Three-Dimensional Printing of MetalParts for Tooling and Other Applications,’ Met. Mater. (Seoul, Rep.Korea), vol. 6, no. 6, pp. 589-594.

2. Budinski, K G & Budinski, M K 1999, Engineering Materials: Propertiesand Selection, 6th edn., Prentice-Hall, Englewood Cliffs, N.J.

3. Conner, B P, Manogharan, G P, Martoff, A N, Rodomsky, L M, Rodomsky,C M, Jordan, D C & Limperos, J W 2014, ‘Making Sense of 3-D Printing:Creating a map of Additive manufacturing Products and Services,’Additive Manufacturing, vol. 1-4, October, pp. 64-76

4. Farid, A, Feng, P, Du, X, Jawid, A., Tian, J & Guo, S 2008,‘Microstructure and Property Evolution During the Sintering of StainlessSteel Alloy With Si3N4,’ J. Mater. Sci. Eng., vol. 472, pp. 324-331.

5. German, R M & D'Angelo, K A 1984, ‘Enhanced Sintering treatments forFerrous Powder,’ International Metals Reviews, vol. 29, no. 1, pp.249-272.

6. Kakisaw, H, Minagawa, K, Ida, K, Maekawa, K & Halada, K 2005, ‘DenseO.M Component Produced by Solid Freefrom Fabrication (SFF),’ MaterialsTransactions, vol. 46, no. 12, pp. 2574-2581.

7. Lanzetta, M & Sachs, E 2003, ‘Improved surface finish in 3D printingusing bimodal powder distribution,’ Rapid Prototyping Journal, vol. 9,no. 3, pp. 157-166.

8. Lorenz, A, Sashs, E, Allen, S, Rafflenbeul, L & Kernan, B 2004,‘Densification of a Powder-Metal Skeleton by Transient Liquid-PhaseInfiltration,’ Metall. Mater. Trans. A, vol. 35A, pp. 631-640.

9. Molinari, A, Kazior, L, Marchetti, F, Canteri, R, Cristofolini I &Tiziani A 1994, ‘Sintering mechanisms of boron alloyed AISI 316stainless steel,’ Powder Metallurgy, vol. 37, no. 2, pp. 115-112.

10. Moon, J, Grau, J E, Cima, M J & Sachs, E M 2000, ‘Slurry chemistrycontrol to produce easily redispersible ceramic powder compacts,’Journal of the American Ceramic Society, vol. 83, no. 10, pp. 2401-3.

11. Riegger, H, Pask, J A & Exner, H E 1980, In: Kuczynski GC (ed)Sintering processes, Plenum Press, New York, pp 219-233.

12. Sun, L., Kim, Y H, Kim, D & Kwon, P 2009, ‘Densification andProperties of 420 Stainless Steel Produced by Three-Dimensional Printingwith Addition of Si3N4 Powder,’ Journal of Manufacturing Science andEngineering, vol. 131, no. 6, doi:10.1115/1.4000335.

13. Warren, R & Waldron, M B 1972, ‘Microstructural development duringthe liquid phase sintering of cemented carbides,’ Powder Metall, vol.15, pp. 166-201.

1. (canceled)
 2. The method of claim 31, wherein the first metalliciron-containing powder and the second metallic iron-containing powder(when present) independently comprise iron-containing metallic alloyparticles.
 3. The method of claim 31, wherein the first metalliciron-containing powder and the second metallic iron-containing powder(when present) independently comprise stainless steel particles.
 4. Themethod of claim 31, wherein the first metallic iron-containing powderand the second metallic iron-containing powder (when present)independently comprise steel particles.
 5. The method of claim 31,wherein the boron-containing powder comprises one or more of elementalboron particles, boron carbide (BC) particles, and boron nitride (BN)particles.
 6. The method of claim 31, wherein the first metalliciron-containing powder and the second metallic iron-containing powder(when present) are together present in an amount from 90 wt. % to 99.99wt. % relative to the sintering composition.
 7. The method of claim 31,wherein the boron-containing powder is present in an amount from 0.01wt. % to 10 wt. % relative to the sintering composition.
 8. The methodof claim 31, wherein the first metallic iron-containing powder, theboron-containing powder, and the second metallic iron-containing powder(when present) are together present in an amount from 90 wt. % to 100wt. % relative to the sintering composition.
 9. The method of claim 31,wherein: the second metallic iron-containing powder is present; and thefirst metallic iron-containing powder and the second metalliciron-containing powder are present in a weight ratio in a range from1:10 to 10:1.
 10. The method of claim 31, wherein: the second metalliciron-containing powder is present; and the first metalliciron-containing powder and the second metallic iron-containing powderhave a different size distribution from each other.
 11. The method ofclaim 10, wherein: the first metallic iron-containing powder and thesecond metallic iron-containing powder have the same composition andtogether form a bimodal size distribution of the same composition. 12.The method of claim 31, wherein the first metallic iron-containingpowder and the second metallic iron-containing powder (when present)independently have a particle size in a range from 1 μm to 100 μm. 13.The method of claim 12, wherein: the first metallic iron-containingpowder has a particle size in a range from 10 μm to 50 μm; and thesecond metallic iron-containing powder is present and has a particlesize in a range from 1 μm to 20 μm.
 14. The method of claim 12, wherein:the second metallic iron-containing powder is present; and the firstmetallic iron-containing powder and the second metallic iron-containingpowder have average sizes in a ratio in a range from 1.5:1 to 10:1. 15.The method of claim 31, wherein the boron-containing powder has aparticle size in a range from 0.01 μm to 20 μm.
 16. The method of claim31, wherein the first metallic iron-containing powder and theboron-containing powder have average sizes in a ratio in a range from5:1 to 100:1.
 17. (canceled)
 18. The method of claim 31, wherein thebinder phase comprises a polymeric binder.
 19. (canceled)
 20. The methodof claim 31, wherein sintering comprises heating to a temperature in arange from 1100° C. to 1300° C.
 21. The method of claim 31, wherein thefused model has a surface roughness less than that of a correspondingfused model formed without the boron-containing powder.
 22. The methodof claim 31, wherein the fused model has a surface roughness in a rangefrom 1 μm to 9 μm.
 23. The method of claim 31, wherein the fused modelhas a density that is greater than that of a corresponding fused modelformed without the boron-containing powder.
 24. The method of claim 31,wherein the fused model has a density of at least 80% relative to thetheoretical density of the sintering composition.
 25. (canceled) 26.(canceled)
 27. (canceled)
 28. (canceled)
 29. (canceled)
 30. (canceled)31. A three-dimensional printing method for forming a fused model, themethod comprising: applying a plurality of successive sinteringcomposition layers, each layer comprising (i) a sintering compositionpowder layer and (ii) a binder applied to at least a portion of thesintering composition powder layer, wherein: the sintering compositionpowder comprises in admixture (a) a first metallic iron-containingpowder, (b) a boron-containing powder, and (c) optionally a secondmetallic iron-containing powder having at least one of a differentcomposition relative to the first metallic iron-containing powder and adifferent size distribution relative to the first metalliciron-containing powder; and collective binder-containing portions of thesintering composition powder in the plurality of successive sinteringcomposition layers defines a selected geometry of the fused model;curing the binder and then removing free sintering composition frombound sintering composition to form a sintering model; and sintering thesintering model to form a unitary fused model from the sinteringcomposition.
 32. The method of claim 31, wherein each sinteringcomposition powder layer has a thickness in a range of 0.01 mm to 5 mm.33. The method of claim 31, wherein curing the binder comprisesperforming one or more of applying heat to the binder, exposing thebinder to light, exposing the binder to oxygen and/or water.
 34. Themethod of claim 31, wherein applying the plurality of successivesintering composition layers comprises: applying successive sinteringcomposition powder layers as successive layers in an adjustable printbed; and applying successive portions of binder with a moveable printhead to the successive sintering composition powder layers.
 35. Themethod of claim 34, wherein at least some of the successive portions ofapplied binder have a different size or a different shape relative toeach other.